J. Chem. Thermodynamics 37 (2005) 459465 www.elsevier.

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Henrys law constants and innite dilution activity coecients of propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene, and 1,3-butadiene in 1-pentanol, 2-pentanol, and 3-pentanol
Yoshimori Miyano
*
Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505, Japan Received 15 July 2004; received in revised form 25 October 2004; accepted 1 November 2004 Available online 13 December 2004

Abstract Henrys law constants and innite dilution activity coecients of propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene, and 1,3-butadiene in 1-pentanol, 2-pentanol in the temperature range of (250 to 330) K and 3-pentanol in the temperature range of (260 to 330) K were measured by a gas stripping method. A rigorous formula for evaluating the Henrys law constants from the gas stripping measurements was used for the data reduction of these highly volatile mixtures. The uncertainty is about 2% for the Henrys law constants and 3% for the estimated innite dilution activity coecients. In the evaluation of the innite dilution activity coecients, the nonideality of the solute such as the fugacity coecient and Pointing correction factor cannot be neglected, especially at higher temperatures. The estimated uncertainty of the innite dilution activity coecients includes 1% for nonideality. 2004 Elsevier Ltd. All rights reserved.
Keywords: Experimental data; Mixture; Henrys law constant; Activity coecient; 1-Pentanol; 2-Pentanol; 3-Pentanol; Propane; Propene; Butane; Isobutane; 1-Butene; Isobutene; trans-2-Butene; 1,3-Butadiene

1. Introduction A systematic study of gas solubilities including the Henrys law constant is useful in providing design data for absorption processes as well as indirectly in aiding the analysis of molecular interactions in solutions. Although a large number of (alkane + alcohol) and (alkene + alcohol) solubility data have been published, few data are available for C4 gases such as butane, 1-butene, and their isomers. The solubility data will be useful in developing prediction methods. Especially for group contribution methods, it may be necessary to take into account the dierences between isomers.
*

Tel.: +81 86 440 1069; fax: +81 86 440 1062. E-mail address: miyano@chem.kusa.ac.jp.

To estimate the gas solubility from a molecular theory or molecular simulation, on the other hand, an accurate intermolecular potential is necessary. The Henrys law constant is directly related to the residual chemical potential of the solute at innite dilution, which is evaluated from the intermolecular potential between a solute molecule and a solvent molecule. Therefore, the Henrys law constant is a suitable macroscopic property for testing the intermolecular potential between dierent kinds of molecules. The gas stripping method, proposed by Leroi et al. [1], has been used to measure the activity coecients at innite dilution of liquid solutes in nonvolatile solvents. In previous work [26], the Henrys law constants for propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene, and 1,3-butadiene in methanol,

0021-9614/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.jct.2004.11.005

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propanols and butanols were measured with this method. For these highly volatile solutes and solvents, a rigorous expression had been derived for data reduction [2]. In this work, the Henrys law constants for propane, propene, butane, isobutane, 1-butene, isobutene, trans2-butene, and 1,3-butadiene in 1-pentanol, 2-pentanol, and 3-pentanol are measured by the gas stripping method, and the innite dilution activity coecients of solutes are evaluated.

2. Theory The gas stripping method, originally proposed by Leroi et al. [1], is based on the variation of the vaporphase composition when the highly diluted solute in a liquid mixture in an equilibrium cell is stripped from the solution by the ow of inert gas (helium). The composition of the gas leaving the cell is periodically sampled and analyzed by gas chromatography (g.c.). The g.c. signal area, S, of the solute decreases exponentially with the volume of inert gas owing out of the cell by the following rigorous relation [2]: 0 1 H g =uV S g   1A ln @ S0 V a H = u 1 aP sat g s g   1 0 V 1 aP sat s a H g =ug   V A; 1 ln @1 V ZRTnL V H = u GP ; 0 g s; 0 g where Hg is the Henrys law constant dened as H g lim
xg !0

Equation (1) requires the assumption that a linear relation between the signal area, S, and the concentration exists. As the concentration of the solute in vapor phase was so diluted, all solutes satised this assumption, and the proportionality constants between the signal area and the partial pressure were experimentally determined for each solute. From equation (1), the Henrys law constant of the solute can be obtained as the slope of the line in a loglog plot as follows: the initial value of the Henrys law constant was set equal to zero, and the logarithm on the right-hand side in equation (1) was calculated. Then the new value of the Henrys law constant was obtained. These calculations were iterated to obtain the constant value of the Henrys law constant. The innite dilution activity coecient of the solute, c1, can be obtained from the following relationship:
sat 1 H g fgL; c1 fgsat kc1 usat g P g kc ;

4 5

c1

Hg sat ; usat g Pg k

where fgL; is the fugacity of the pure solute at the reference state (pure liquid at the system temperature and pressure), fgsat and usat g are the fugacity and the fugacity coecient of the pure solute at the saturation, P sat g is the vapor pressure of the solute at the system temperature, and k is the Poynting correction factor, and is well approximated as ! L;sat P P sat g mg k % exp ; 6 RT where P is the system pressure. The vapor pressures and the saturated liquid densities for pure substances were evaluated from the data book [7]. The thermodynamic properties appearing in the above equations, sat uV g ; ug ; Z , and so forth, were calculated by the virial equation of state truncated after the second virial coecient. For propane and propene, however, the virial equation of state truncated after the third virial coecient was used for this purpose because of its high volatility. The details of the calculation methods were described in the previous papers [2,3].

fgV ; xg

fgV is the fugacity of the solute in vapor phase, xg is the mole fraction of the solute in the liquid phase, the subscript g indicates the solute. S0 is the signal area of the solute at time t = 0, P sat s is the saturated vapor pressure of the pure solvent (s), Z is the compressibility factor of the saturated vapor in the cell, and uV g represents the fugacity coecient of the solute in the vapor phase. Superscripts V and L denote vapor and liquid phases, respectively. nL s;0 is the number of moles of solvent in the liquid phase in the cell at t = 0. VGP,0 is the initial volume of the vapor phase in the cell, and V is the volume of the saturated gas owing out of the cell. The volume of the vapor phase in the cell at time t, VGP, slightly depends on the gas volume withdrawn from the cell, and it is expressed as V GP V GP;0 aV ; a
L;sat P sat s ms ; ZRT

3. Experimental Details of the experimental apparatus were presented in our earlier paper [2,5]. About 36 cm3 of the solvent (pentanols) was introduced into the equilibrium cell (volume % 40 cm3), and the accurate quantity was determined by mass. Then the equilibrium cell was immersed in a constant-temperature bath (lled with ethylene glycol + water) and connected to a supply of helium. The temperature was controlled to within 0.02 K and meas-

;sat where mL is the liquid molar volume of the solvent at s saturation, R is the gas constant, and T is the absolute temperature.

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ured with a quartz thermometer (HewlettPackard Co., Model 2804A) with an accuracy of 0.01 K. About 1 cm3 of the solute gas was introduced into the equilibrium cell by a syringe. The amount of the solute gas introduced into the cell was adjusted to keep the mole fraction lower than 104 in solution. Then, helium began to ow into the equilibrium cell at a ow rate of about 2 cm3 min1 which was measured with a mass ow meter (Kooc Co., Model 3300) with a maximum ow rate of 2 cm3 min1 and an accuracy of 1%. The ow rate was controlled with a ne metering valve (double needles, Swagelok Co., SS2-D). The gas owing out of the equilibrium cell was kept at a higher temperature than that of the bath to avoid any condensation and was introduced into a gas chromatograph (Hitachi Ltd., Model G-3000, with double FID detectors) to measure the solute signal area, S. Sampling for the gas chromatography was performed every 60 min and continued for about 20 h. The pressure in the cell, the temperatures of the bath, and the total number of moles of helium, nHe, which could be obtained from the integration of the ow rate, were also measured every 60 min. The pressure in the cell was approximately equal to atmospheric pressure, and atmospheric pressure was measured by a pressure transducer (Paroscientic, Inc., Digiquartz pressure transducer Model 215A and Tsukasa Sokken Co. Ltd., Digiquartz Pressure Computer Model 600S) to an accuracy of 10 Pa. The uncertainty of this measurement for the Henrys law constants may be considered to be within 2%; it mostly depends on the accuracy of the mass ow meter. 3.1. Materials Butane, isobutane, 1-butene, and isobutene were supplied by Takachiho Kagaku Kogyo with specied minimum mass fraction purities of 0.998, 0.99, 0.99, and 0.99, respectively. Propane and propene were supplied by Japan Fine Products at specied minimum mass fraction purities of 0.995 and 0.995, respectively. trans-2-Butene and 1,3-butadiene were supplied by Aldrich Chemicals at specic minimum mass fraction purities of 0.99 and 0.99, respectively. 1-Pentanol was supplied by Kishida Chemical Co. with specied minimum purities of 98+% by gas chromatography. The both of 2-pentanol and 3-pentanol were supplied by Tokyo Kasei Kogyo Co. with specied minimum purities of 98+% by gas chromatography. All materials were used without further purication.

anol, and 3-pentanol systems, respectively. Because all experiments were conducted under atmospheric pressure, the estimated fugacity coecients of the solute in the vapor phase and the compressibility factors of the vapor were around unity (uV g 1, Z = 1) for all systems. However, for the evaluation of the innite dilution activity coecients, the nonideality of gases at saturation
TABLE 1 Henrys law constants and innite dilution activity coecients of solutes in 1-pentanol T/K 249.96 269.99 290.00 310.00 330.00 249.96 269.99 290.00 310.00 330.00 249.97 270.01 290.00 310.00 330.00 249.97 270.01 290.00 310.00 330.00 249.96 269.99 290.00 310.00 330.00 249.97 270.01 290.00 310.00 330.00 249.96 269.99 290.00 310.00 330.00 249.97 270.01 290.00 310.00 330.00 Hg/kPa 630 1200 2050 3180 4500 660 1230 2060 3160 4410 132 295 580 1032 1650 223 475 890 1510 2300 140 314 610 1050 1650 142 316 620 1060 1630 101 235 467 840 1350 113 259 510 890 1380 c1 Propane 3.08 3.07 3.08 3.05 3.00 Propene 2.59 2.59 2.60 2.59 2.51 Butane 3.43 3.33 3.31 3.27 3.19 Isobutane 3.65 3.59 3.56 3.51 3.40 1-Butene 2.88 2.87 2.82 2.78 2.70 Isobutene 2.86 2.84 2.82 2.76 2.63 trans-2-Butene 2.80 2.80 2.76 2.76 2.69 1,3-Butadiene 2.50 2.51 2.50 2.46 2.33 P sat g =kPa 218 432 771 1275 1986 273 530 935 1531 2367 39.2 91.8 188 347 592 63.0 140 273 486 803 49.7 114 230 420 707 50.5 116 234 427 719 36.6 86.7 179 333 568 46.1 107 218 400 678 usat g 0.94 0.92 0.89 0.85 0.82 0.94 0.91 0.87 0.84 0.80 0.98 0.96 0.94 0.92 0.89 0.97 0.95 0.93 0.90 0.87 0.98 0.96 0.94 0.91 0.88 0.98 0.96 0.94 0.91 0.88 0.98 0.97 0.95 0.92 0.90 0.98 0.96 0.94 0.92 0.89

4. Results and discussion The Henrys law constants and the innite dilution activity coecients measured in this work are numerically indicated in tables 1 to 3 for the 1-pentanol, 2-pent-

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Y. Miyano / J. Chem. Thermodynamics 37 (2005) 459465 TABLE 3 Henrys law constants and innite dilution activity coecients of solutes in 3-pentanol T/K 259.96 270.02 280.00 290.00 300.00 310.01 320.00 330.00 259.94 270.02 280.00 290.00 300.00 310.01 320.00 330.01 259.98 270.02 280.00 290.00 300.00 310.01 320.00 330.01 259.96 270.02 280.00 290.00 300.00 310.01 320.00 330.01 259.96 270.02 280.00 290.00 300.00 310.01 320.00 330.00 259.96 270.02 280.00 290.00 300.00 310.01 320.00 330.01 259.96 270.02 280.00 290.00 Hg/kPa 940 1250 1620 2060 2540 3020 3560 4110 1040 1360 1750 2170 2620 3090 3570 4080 207 301 426 580 750 960 1190 1440 335 480 650 870 1110 1380 1680 2020 243 347 475 640 830 1030 1260 1520 245 350 481 640 830 1030 1260 1500 174 257 357 486 c1 Propane 3.27 3.21 3.14 3.09 3.01 2.90 2.81 2.72 Propene 2.97 2.87 2.82 2.74 2.63 2.53 2.42 2.32 Butane 3.48 3.40 3.36 3.26 3.15 3.04 2.92 2.79 Isobutane 3.66 3.62 3.53 3.45 3.35 3.22 3.09 2.98 1-Butene 3.27 3.16 3.05 2.96 2.86 2.72 2.61 2.49 Isobutene 3.25 3.15 3.04 2.93 2.82 2.69 2.56 2.43 trans-2-Butene 3.12 3.06 2.96 2.88 P sat g =kPa 311 432 583 771 1000 1275 1601 1986 385 531 712 935 1207 1532 1916 2367 61.1 91.8 133 188 258 347 458 592 95.3 140 198 273 368 486 630 803 76.7 114 165 230 314 420 550 707 77.9 116 167 234 319 427 559 719 57.4 86.8 127 179 (continued on next usat g 0.93 0.92 0.90 0.89 0.87 0.85 0.84 0.82 0.92 0.91 0.89 0.87 0.86 0.84 0.82 0.80 0.97 0.96 0.95 0.94 0.93 0.92 0.90 0.89 0.96 0.95 0.94 0.93 0.91 0.90 0.88 0.87 0.97 0.96 0.95 0.94 0.93 0.91 0.90 0.88 0.97 0.96 0.95 0.94 0.92 0.91 0.90 0.88 0.97 0.97 0.96 0.95 page)

TABLE 2 Henrys law constants and innite dilution activity coecients of solutes in 2-pentanol T/K 249.93 269.99 290.00 310.00 0330.00 249.93 269.99 290.00 310.00 330.00 249.93 269.96 290.00 310.00 330.00 250.01 269.96 290.00 310.00 330.00 249.94 269.99 290.00 310.00 330.00 249.94 269.98 290.00 310.00 330.00 249.94 269.99 290.00 310.00 330.00 249.94 269.98 290.00 310.00 330.00 Hg/kPa 640 1220 2020 3020 4180 710 1310 2110 3090 4160 131 298 570 980 1520 225 478 880 1420 2100 148 331 620 1020 1520 153 333 620 1010 1520 104 244 474 810 1250 136 297 550 900 1340 c1 Propane 3.13 3.12 3.02 2.90 2.76 Propene 2.79 2.77 2.66 2.53 2.37 Butane 3.40 3.38 3.24 3.11 2.94 Isobutane 3.66 3.61 3.49 3.30 3.10 1-Butene 3.04 3.03 2.86 2.69 2.50 Isobutene 3.10 2.99 2.82 2.63 2.45 trans-2-Butene 2.90 2.91 2.81 2.65 2.49 1,3-Butadiene 3.01 2.89 2.68 2.47 2.27 P sat g =kPa 218 432 771 1275 1986 272 530 935 1531 2367 39.1 91.6 188 347 592 63.1 139 273 486 803 49.7 114 230 420 707 50.5 116 234 427 719 36.6 86.7 179 333 568 46.0 107 218 400 678 usat g 0.94 0.92 0.89 0.85 0.82 0.94 0.91 0.87 0.84 0.80 0.98 0.96 0.94 0.92 0.89 0.97 0.95 0.93 0.90 0.87 0.98 0.96 0.94 0.91 0.88 0.98 0.96 0.94 0.91 0.88 0.98 0.97 0.95 0.92 0.90 0.98 0.96 0.94 0.92 0.89

is not negligible. For highly volatile solutes such as propene, the vapor pressure at T = 330 K is about P = 2400 kPa, and the nonideality should be evaluated. The estimation uncertainty for the nonideality was about 1% as discussed in the previous paper [2]. Therefore, it is considered that the uncertainty of the obtained

Y. Miyano / J. Chem. Thermodynamics 37 (2005) 459465 TABLE 3 (continued) T/K 300.00 310.01 320.00 330.01 259.98 270.02 280.00 290.00 300.00 Hg/kPa 640 810 1000 1250 221 313 430 560 720 c1 2.77 2.67 2.54 2.50 1,3-Butadiene 3.18 3.03 2.92 2.75 2.63 P sat g =kPa 247 333 439 569 71.5 107 155 218 298 usat g 0.94 0.92 0.91 0.90 0.97 0.96 0.95 0.94 0.93

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innite dilution activity coecients may be considered to be no greater than 3%. Figures 1 to 3 show the temperature dependency of the Henrys law constants of the eight gases in 1-pentanol, 2-pentanol and 3-pentanol, respectively. Only the gas solubilities of propene and isobutene in 1-pentanol at T = 293.15 K and P = 101.325 kPa by Narasimhan et al. [8] are available in the literatures. The Henrys law constants estimated from their gas solubility data deviate about 30% to 100% from our data as shown in gure 1. This suggests that it is dicult to obtain the Henrys law constants from only one solubility datum at atmospheric pressure. The order of the Henrys law constants of the eight gases in 1-pentanol at T = 290 K is as follows: propene (Tb = 225.5 K) > propane (231.1 K) > isobutane (261.4 K) > isobutene (266.2 K) % 1-butene (266.9 K) > butane (272.7 K) > 1,3-butadiene (268.7 K) > trans-2-butene (274.0 K). The same order is observed for the 2-pentanol and 3-pentanol systems. The Henrys law constants of nonpolar gases in nonpolar solvents generally follow

FIGURE 2. Henrys law constants of eight gases in 2-pentanol (s, propane; m, propene; h, butane; , isobutane; ,, 1-butene; d, isobutene; , trans-2-butene; }, 1,3-butadiene).

the order of increasing Henrys law constant with decreases in the normal boiling temperature (Tb) of the liqueed gas. This means that 1-pentanol, 2-pentanol, and 3-pentanol can be approximately treated as nonpolar solvents. The molecular size of 1,3-butadiene is smaller than others because it has two double bonds, which will make it easier to insert the molecule into a liquid. As the result, the Henrys law constant of the smaller size molecule becomes smaller in general. This may be the

FIGURE 1. Henrys law constants of eight gases in 1-pentanol (s, propane; m, propene; h, butane; , isobutane; ,, 1-butene; d, isobutene; , trans-2-butene; }, 1,3-butadiene; x, propene [8]; n, isobutene [8]).

FIGURE 3. Henrys law constants of eight gases in 3-pentanol (s, propane; m, propene; h, butane; , isobutane; ,, 1-butene; d, isobutene; , trans-2-butene; }, 1,3-butadiene).

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FIGURE 4. The innite dilution activity coecients of eight gases in 1-pentanol (s, propane; m, propene; h, butane; , isobutane; ,, 1-butene; d, isobutene; , trans-2-butene; }, 1,3-butadiene).

FIGURE 5. The innite dilution activity coecients of eight gases in 2-pentanol (s, propane; m, propene; h, butane; , isobutane; ,, 1-butene; d, isobutene; , trans-2-butene; }, 1,3-butadiene).

reason that 1,3-butadiene does not follow the simple relationship described above. Figures 4 to 6 show the temperature dependency of the innite dilution activity coecients for the same systems. The temperature dependency of the innite dilution activity coecients is negligibly small for 1pentanol system, but it becomes larger for 2-pentanol and 3-pentanol systems as shown in these gures. Especially, the temperature dependency of the innite dilution activity coecients of 1,3-butadiene strongly depends on the solvents. The innite dilution activity coecients of 1,3-butadiene in 1-pentanol can be approximated as a constant value as shown in gure 4. On the other hand, the innite dilution activity coecients of 1,3-butadiene in 2-pentanol and 3-pentanol decrease very quickly with increasing of the temperature. From a viewpoint of a molecular simulation of the Henrys law constant, it is considered that the volume change of the solvent may cause a drastic change of the probability of the insertion of a solute molecule into the solvent. Therefore, the volume change of the solvent may cause the strong temperature dependency of the Henrys law constant and the innite dilution activity coecient. For example, the molar volumes of 1-pentanol are 105.0 cm3 mol1 at T = 260 K and 112.08 cm3 mol1 at T = 330 K. This causes the change of the molar volume of 7.0 cm3 mol1. The changes of the molar volume of 2-pentanol and 3-pentanol at the same temperature range are (7.8 and 8.0) cm3 mol1, respectively. The volume changes of 2-pentanol and 3-pentanol are about 12% larger than that of 1-pentanol. This may be

the reason why the temperature dependency of the innite dilution activity coecients of gases in 2-pentanol and 3-pentanol is larger than that in 1-pentanol. As described in the previous paper [5], it is dicult to apply this experimental apparatus to the measuring of the Henrys law constants of gases in highly viscous uids, because of the increasing diculty of the mixing of the vis-

FIGURE 6. The innite dilution activity coecients of eight gases in 3-pentanol (s, propane; m, propene; h, butane; , isobutane; ,, 1-butene; d, isobutene; , trans-2-butene; }, 1,3-butadiene).

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cous uid. For the 3-pentanol system, it was dicult to get good reproducible data at T = 250 K because of its high viscosity. For the (1,3-butadiene + 3-pentanol) system, it was also dicult to get good reproducible data at higher temperatures than 300 K. A kind of chemical reaction may be occurred at higher temperatures. The innite dilution activity coecients for C4 gases in methanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol could be classied into three groups. The rst group was the alkane (butane and its isomers). The second was the alkene (1-butene and its isomers), and the last group was the dialkene (1,3-butadiene). Each group showed very close values of the innite dilution activity coecients, and the order of the innite dilution activity coecients was alkane > alkene > dialkene for C4 gases. The similar phenomena can be observed for 1-pentanol, 2-pentanol, and 3-pentanol systems.

The Henrys law constants of the eight gases in the three alkanols studied here have followed the order of increasing Henrys law constant with decreases in the normal boiling temperature of the liqueed gas, except for 1,3-butadiene. The temperature dependency of the innite dilution activity coecients of gases in 1-pentanol has been smaller than those in other two alkanols.

Acknowledgement This paper reports part of the work supported by a Grants-in-Aid for Scientic Research from the Japan Society for the Promotion of Science (16560663), which is gratefully acknowledged.

References 5. Conclusions Henrys law constants and the innite dilution activity coecients of eight gases in 1-pentanol, 2-pentanol in the temperature range of (250 to 330) K and 3-pentanol in the temperature range of (260 to 330) K have been obtained from gas stripping measurements. The Henrys law constant did not depend on the nonideality of the vapor for the systems studied in this work. On the other hand, the nonideality of the solute at the reference state should be considered in order to obtain innite dilution activity coecients precisely.
[1] J.-C. Leroi, J.-C. Masson, H. Renon, J.-F. Fabries, H. Sannier, Ind. Eng. Chem., Process Des. Dev. 16 (1977) 139144. [2] Y. Miyano, K. Nakanishi, K. Fukuchi, Fluid Phase Equilibr. 208 (2003) 223238. [3] Y. Miyano, J. Chem. Thermodyn. 36 (2004) 101106. [4] Y. Miyano, J. Chem. Eng. Data 49 (2004) 368371. [5] Y. Miyano, J. Chem. Eng. Data 49 (2004) 12851289. [6] Y. Miyano, J. Chem. Thermodyn. 36 (2004) 865869. [7] B.D. Smith, R. Srivastava, Thermodynamic Data for Pure Compounds: Part A and Part B, Elsevier, Amsterdam, 1986. [8] S. Narasimhan, G.S. Natarajan, G.D. Nageshwar, Indian J. Technol. 19 (1981) 298299.

JCT 04-160